Casein size and method of producing same



Patented Aug. 26, 1924.

annum n.

BEGINALD winnen, 0F Familienaam, nAssncHUsET'rs.

CASEIN SIZE AND METHOD 0F PODUCING .Y

No Drawing.

To all whom 'it may concern:

Be it known that I, ADRIEN a citizen of the United States, residin at Revere, in the county of Suffolk and tate of Massachusetts, have inventednew and useful Improvements in Casein Size and E. Redman,v

k'Methods off Producing 4the Same, of which the following is a specification."

This invention has for its object to produce a size for use inthe treatment of paper, either for coating the same lor for admxture with coloring matter in the printing of wall paper.

As is well known, casein, as produced commercially, vhas been used for paper sizing, but it has not heretofore been ossble to use it in wall papers, for examp e, wherein the coloring matter, used `for coatingA or rnting the paper, has an acid reaction.

his is due to the fact that, in the conversion of the casein which is normally water- `ins`eluble, into an aqueous adhesive solution,

it has been necessary to convert or digest the casein with an alkali ofthe nature. of ammonia, sodium carbonate, sodium boratecr trisodium phosphate, so that the solution is distinctl-yalltaline in4 reaction. Consequently, when-'Tan alkaline casein solution is.

brought into contact Awith the pulp con-` taining' the coloring matter and' having an acidl -vreaction, fthe acid `had a coagulating action on* thefcaseinfandthe alkalijin the caseinhad a tendency to neutralize the acid infthecoloring matter and to change the color thereof. For example, the ulp so-` called, used in the production rof wa l papers, contains in most cases barium chloride,v or sodium sulphate, and aniline dye; and,when such pulp comes in contactA with .the casein solution, as. for exam le when a` green c olored pulp s'employe the casein is Coil/gu', lated and precipitated, and, Yif sulicienl;

alkali" to preventcoagulation is used, the color of the` pulp gradually changes from en to yellowish green. Consequently it as heretoforefbeen universally 4the pracn tice, in the production of wall pape-rs and.l

the like, to employ asize consisting of animal glue or a starch glue. Since such glues are watereoluble, the .resultis that, when` wall papers are wet, the colors run, and in .Origilmlly'` precipita apprese@ and auguran, 1921. semi releases.

addition it is eas yeven when the f apers are dry, to oA or remove matter from 'the surface thereofl The present ,invention has for its object to produceva casein si'ze, which` is water-insoluble when dry 'andifv'ith' which the ordianGNIEn, o1" nnvnan; nnssncnusms, nssmnoa or oma-nam?I ToV ,heV co orig l nar'y coloring mattersr pulp may' be used.

Iliavf' `-found that casein, which has been original y coagulated anddprecipitated by hy rochloric acid, may be 'convertedto an aqueous paste by sodium fluoride, the' vi-scoslty of the product depending upon the' quan tlty of Water used; and that the si thus `f produced may be used for' coatingf papers or for admixtujrc' with thepulp Aorcivlorin matterfor coating or printing paper.V Wit Iless'beneicial results casein,"which has been te by sul huric acid d and Lthe curd 'cooked,fmay also` ei cbnverted into an aqueous'solution f or the uses mentioned; but, inas'mchas the casein is more diiiicultly conyerted"V the solutonmu'st be strainedfto reniovet e'unconirernted portions production. When the casein siz'ef" as "tilnis been .produced the conversion of the casein with sodium uo'ide, the Ysite has an' acid reaction,` .andy consequently the acid 'of the coloring matterfhas" no coagulating or cipita'lzirig` e'ect thereon,A @11d the size? not 1n turn. have any chemical reaction'with` the coloring matter. When the wate'rvis' 17emoved from the size, 'thev casein yis, 'wa'terA resistant or waterfinsolublg thereby "tend in 'to make water-,resistant,tliepaperor the co orlng matter with which itk is mixed.

skimmedmilkis permitted. to" sour to` acerf tain Lpoint Y of acidity,l whereupon hydro` Chlor-1c acid is added and stirred*.into1 *the In the initial 'productionr of the casein, the" milk v,thoroughly?h with the result' that the ter, nor is there a precipitation or coagulais cooked in accordance with the usual process and then pressed and dried as previously described. o y

As an example of practicin my process, one may proceed as follows: o 100 uds of commercial casein, produced as ereinbefore described, ma of water and a suita le quantit of sodium uoride,-say 8 to 16 ounds. he quantity of sodium uoride which may be used varies within relatively wide ranges. These ingredients are mixed together at ordinary temperature in a mixin vat with suilicientu a 'tation to ensure.,a t loroughmadmixture. e action of the sodium yFluoride on the casein is to convert it with water into a solution, the viscosity ,of which depends upon the quantity of water employed. To hasten the conversiomthe mixture may be heated during the agitation, to a Itemperature oi about 160 F., after which it is permitted to cool to about 90 Kli. 'The size, which is thus roduced, may be paper, or it may be mixe with the nlp or coloring matter in suitable roportions. The mixture may be employ forsurface coating or i may he used in the printing of designs.

Ordinarily, for shipment, the casein is mixed with a suitable pro ortion of sodium liuoride ina dry form an shipped as a base in this condition to the place of use, where water may be.` added andthe processA reviously described followedfor the pro uction of the size. The size thus produced may thus be used in ,the coating or printing of. wall paper, or employed for sizing, coating or printing of various kinds of paper.

nasmuch as the` size has an acid reaction, there isas previously stated lno chemical reaction between the size and the ycoloring mattion ofthe casein dueto the presence of acids in the coloring matter. Sometimes it is desirable to increase the ,fiowin'g propertiesof the size, and for this purpose various suitable materials may be added thereto. For example,I1 I have discovered that ammonium oxa ate o'r trisodium phosphate, or lessV bei'iecial results potassium oxalate, may be employed for the purpose. While the viscosit of the size may be decreasedby thea dition of water thereto,l

nevertheless water also decreases the adhesive properties thereof 5 whereas, by using ammonium oxalate or trisodium phosphate, the viscosity of the size may be decreased without decreasing its adhesiveness. In particular, ammonium oxalate has the pro erty of retarding the coagulation o t e coloring matter with whichy the size is mixed and permits it to he spread more uniformly in coatin or printing, vThese materials, thus ul for increasing the `flowing properties of the size, may be added in a dry state to the base or mixture of casein and be added 400 pounds4 y y `heretofore been secured in those sizes wheresodium fluoride for shipment to the point of use.

One of the decided advantages, incident to a size such as herein describedxis that it is freeilowing and producesL asinooth, satiny finish. It enables one to obtain a finer finish when used as a size or coatin than has in casein has been emplo ed asthe base material. For example, w en used as a size with satin white so-called, a much liner and more velvety finish is secured than has heretofore been possible. When used with bronze, steel blue, co per bronze or the like, the size, owing to its aving an acid reaction, increases Aand brings out the brightness or the luster or the iinishing properties of the materials named.

A composition, such asy herein described, has many other uses. which .will readily suggest themselves to those skilled in the art. What I claim is 1. The herein described process of producing a size or glue which consists in dissolving anacid-precipitated casein with sodium fluoride in the presence of water into a Huid adhesive state.

2. The process of producing a size or glue which comprises agitatingamixture of acidprecipitated casein, sodium fluoride, and water at an elevated teliiserature.

3. A process of I ucin a size or glue, which comprises. e coa ation and pre cipitation of caseinwith ydrochloric acid, followed by the drying of the precipitated casein, and the conversion of such casein into an adhesive state the use of sodium fluoride." i

4. A process of Vproducing a free-flowing size, which comprises converting, casein hav- 'ing an acid reaction with'sodium fluoride in the presence of a substance` whichgives to the product the-property of;free flowing.

5,'A process of prcsducing,r a free-flowing size, which comprises oonvertingcasein having a non-alkaline reaction with lsodium iuoride in the presence: of ammonium `oxa-` ate.

6. A non-alkaline size or glue consisting of acid-precipitated casein conve into adhesive condition byv sodium -uoride in the presence of water.- i

7. An adhesive size or glue consisting of an aqueous solution of mineral-acid-precipitated casein and sodium iiuoride 8. An adhesive size or glue consisting of an aqueous solution of casein, sodium iluoride and a substance whichldecreases the viscosity of the size without decreasing its adhesiveneSS.

9. A base for the manufacture of an adhesive size comprising a dry mixture of mineral-acid-precipitated casein and sodium iiuoride.

10. A base for the manufacture of an adhesive size conmstm of a dry mixture of casein, sodium iluori e and ammonium oxelate.

11. A base for the menufectu of an adhesive size or glue, comprising e dry mixture of hydrochloric-wid-precipltated casein, and sodium fluoride.

12. A bese for the msnxzfscture of ln sdhesive size or glue, consisting of s dry mixture of h drochloric-mid-pmcipiteted casein, l0

sodium uoride, and 4ammonium oxalste.

13. A coated or printed product in which the costing or printing composition includes a non-alkaline size compr-isi casein converted into a soluble state by In testimony whereof I have aixed my signature.

ADRIEN E. REGNIER.

ium fluoride. 1l 

